Co-formulation composition

Abstract

The present invention relates to a co-formulation composition comprising a terpenic oligomer and a terpenic alcohol, a phytosanitary and / or biostimulant composition containing the co-formulation and one or more phytosanitary and / or biostimulant active substance(s) and methods of use thereof.

Description

[0001] CO-FORMULATION COMPOSITION

[0002] The present invention relates to a co-formulation composition comprising a terpenic oligomer and a terpenic alcohol, a phytosanitary and / or biostimulant composition containing the co- formulation and one or more phytosanitary and / or biostimulant active substance(s) and methods of use thereof.

[0003] BACKGROUND

[0004] The present invention relates to the field of crop protection products.

[0005] Typically, a crop protection product consists of a composition containing an active substance that is formulated with several co-formulants. This composition is generally applied by spraying. The choice of the co-formulants in the composition play a key role in the effectiveness of the active substance.

[0006] Sulfur is a fertilizer and fungicide commonly used as an active substance in agriculture.

[0007] The skilled person continually seeks to reduce the quantity of active substances for a same efficiency of action in order to reduce their secondary effects such as phytotoxicity. In the particular case of sulfur, the optimization of the quantity of sulfur used aims at limiting its transformation into a product having a phytotoxicity, such as sulfuric acid which can appear under certain conditions. To achieve this, the person skilled in the art can play on parameters such as rain resistance, droplet drying and penetration of the active substance into the plant.

[0008] The present invention aims to overcome these drawbacks by proposing a co-formulation composition allowing the preparation of efficient phytosanitary and / or biostimulant compositions for plant treatment.

[0009] The inventors have discovered a new co-formulation of adjuvants that increases spray retention by sticker effect, improves rainfastness, delays droplet drying and increases active substance penetration in plant. The inventors have also discovered that the new co- formulation allows an enhanced selectivity and / or reduced phytotoxicity, in particular with regard to an active substance such as fungicides. More particularly, the object of the invention is a co-formulation composition of a terpenic oligomers such as Derphalin® and an alcohol terpenic such as Dertol® or dihydromyrcenol.

[0010] The present invention increases efficient part of sprayed plant active substance(s). This co- formulation composition allows active substances rate reduction. It also ensures a good efficacy level under suboptimal application conditions, so it reduces application failure risks. It also allows an enhanced selectivity and / or reduced phytotoxicity, in particular with regard to an active substance such as fungicides. The inventive co-formulation composition of adjuvants also reduces spray drift. Thus, composition formulated with the co-formulation composition of the invention reduces the negative impact on environment and the risk for human health.

[0011] DISCLOSURE OF THE INVENTION

[0012] One object of the present invention relates to a co-formulation composition comprising a terpenic oligomer and a terpenic alcohol.

[0013] Preferably, the co-formulation composition, is an artificial co-formulation composition. Thereby, it is understood that the co-formulation is formulated by combining a terpenic oligomer and terpenic alcohol which are not combined in a natural composition such as an essential oil.

[0014] Preferably, the co-formulation composition is a co-formulation which is not an essential oil.

[0015] Preferably, in the co-formulation composition, the weight ratio of terpenic alcohol to terpenic oligomer ranges from 0.5 to 8, preferably from 0.8 to 6, more preferably from 1 to 4.

[0016] Preferably, in the co-formulation composition, the terpenic oligomer is a molecule containing from 2 to 20 of terpenic structural units, wherein the terpenic structural units correspond to any terpene derived from hydrocarbon isoprene (CsHs)n with n a number ranging from 1 to 8.

[0017] Preferably, in the co-formulation composition, the terpenic oligmer is a molecule terpenic oligomer is a molecule containing from 2 to 20 of terpenic structural units, more preferably 2 to 10 terpenic structural units, wherein the terpenic structural units correspond to any terpene derived from hydrocarbon isoprene (CsHs)n with n a number ranging from 2 to 8 and which is not further functionalized by any heteroatomic groups, such as hydroxy groups, amine groups or sulfur groups.

[0018] Preferably, in the co-formulation composition, the terpenic oligomer is an oligomer of pinene, more preferably an oligomer of alpha- and beta-pinene.

[0019] Preferably, in the co-formulation composition, terpenic oligomer is obtained from a plant such as tree and typically from conifers, in particular from pine trees.

[0020] Preferably, in the co-formulation composition, the terpenic alcohol is a terpen having one or more primary, secondary or tertiary alcohol, preferably selected from the group consisting of

[0021] 2.6-dimethyloct-7-en-2-ol, 4(8)-p-menthen-l-ol, cis-3,7-dimethyl-2,6-octadien-8-ol, trans-

[0022] 3.7-dimethyl-2,6-octadien-l-ol, 10-hydroxymethylene-2-pinene, 3,7-dimethyloct-6-en-l-ol and terpineol isomers such as alpha terpineol, beta terpineol, gamma terpineol, delt terpineol, terpinene-4-ol and a mixture thereof.

[0023] Preferably, in the co-formulation composition, the terpenic alcohol is obtained from plant such as a citrus oils or pine terpenes.

[0024] Another object of the invention relates to a phytosanitary and / or biostimulant composition comprising a co-formulation composition as described above and one or more phytosanitary and / or biostimulant active substance(s).

[0025] Preferably, the composition comprises from 1 to 10 wt. % of terpenic oligomer, preferably from 2 to 8 wt. % of terpenic oligomer and more preferably from 3 to 6 wt. % of terpenic oligomer, expressed by weight relative to the weight of the composition.

[0026] Preferably, the composition comprises from 10 to 70 wt. % of active substance(s), preferably from 30 to 65 wt. % of active substance(s) and more preferably from 50 to 60 wt. % of active substance(s) with respect to the total weight of composition.

[0027] Preferably, the composition comprises an active substance selected from the group consisting of insecticide, bactericide, fungicide, insect repellent or attractant and mixtures thereof.

[0028] Preferably, in the composition, the active substance is selected from the group consisting of sulfur, copper such as copper hydroxide, copper sulfate, copper oxychloride, pelargonic acid, orange essential oil and a mixture thereof.

[0029] Preferably, the composition comprises one or more ingredients selected from the group consisting of a surfactant anionic or not, a polyol, glycerol, an anti-foam agent, a pH regulator and a mixture thereof.

[0030] Preferably, the composition comprises terpenic alcohol from 1 to 10 wt. %, preferably of 2,6-dimethyloct-7-en-2-ol; terpenic oligomer from 1 to 10 wt. %, preferably Derphalin®; active substance from 20 to 70 wt. %, preferably selected from the group consisting of sulfur, copper such as copper hydroxide, copper sulfate, copper oxychloride, pelargonic acid, orange essential oil and a mixture thereof; and eventually one or more of ingredients selected from the group consisting of: anionic surfactant from 1 to 2 wt. %, preferably tristyrylphenol anionic; and / or polyol from 1 to 5 wt. %, preferably propylene glycol; and / or non-ionic surfactants from 1 to 20 wt.%, and / or glycerol from 1 to 5 wt. %, preferably from 2 to 4 wt. % of propylene glycol and from 1 to 3 wt. % of glycerol; and / or anti-foam agent from 0.01 to 1 wt. %, a silicon emulsion; and / or pH regulator from 0.1 to 1 wt.%, preferably sodium hydroxide; and / or and a mixture thereof; water qsp 100 wt. %.

[0031] Preferably, the composition is formulated in the form of a liquid, suspension, an emulsion, a concentrated emulsion, a dispersion, a suspoemulsion, an emulsifiable concentrate or slurry of particles in an aqueous medium.

[0032] Another object of the invention relates to the use of a co-formulation composition as described above for preparing a phytosanitary and / or biostimulant composition as described above.

[0033] Another object of the invention relates to the use of a co-formulation composition as described above for improving

[0034] - spray retention explained by sticker effect; and / or

[0035] - rainfastness; and / or

[0036] - active substance penetration in plant; and / or

[0037] - delay of droplet drying; and / or

[0038] - preservation against UV photodegradation; and / or

[0039] - drift reduction; and / or

[0040] - reducing the phytotoxicity; and / or

[0041] - enhancing the selectivity of the one or more phytosanitary and / or biostimulant active principle(s).

[0042] Another object of the invention relates to a method of treating plant by application of a phytosanitary and / or biostimulant composition as described above.

[0043] Another object of the invention relates to a method of preparation of a phytosanitary and / or biostimulant composition as described above.

[0044] DETAILED DESCRIPTION

[0045] One aspect of the invention concerns a co-formulation composition of a terpenic oligomer and a terpenic alcohol. This co-formulation composition can be used to prepare a phytosanitary and / or biostimulant composition. Typically, the co-formulation composition can be involved in the preparation of a phytosanitary and / or biostimulant composition for plant treatment, particularly as biocontrol fungicide, fertilizers and seed treatment.

[0046] The present invention also relates to a phytosanitary and / or biostimulant composition comprising an active substance and a co-formulation composition of a terpenic oligomers and a terpenic alcohol. Terpenes are chemical compounds that are widespread in nature, mainly in plants as constituents of essential oils. Their building block is the hydrocarbon isoprene (CsHs)n with n an integer ranging from 1 to 8. Terpenes are called monoterpenes (Cio) when n equals 2, sesquiterpenes (Cis) when n equals 3, or again diterpenes (C20) when n equals 4. For example, typical terpenes are citral, pinene, nerol, b-ionone, geraniol, carvacrol, eugenol, carvone, terpeniol, anethole, camphor, menthol, limonene, nerolidol, farnesol, phytol, carotene (vitamin Al), squalene, thymol, tocotrienol, perillyl alcohol, borneol, myrcene, simene, carene, terpenene, and linalool.

[0047] Co-formulation composition

[0048] According to the invention, the co-formulation composition comprises a terpenic oligomer.

[0049] The term "oligomer" is used herein to refer to any molecule containing 2 or more repeating terpenic structural units. Advantageously, the term "oligomer" refers to any molecule containing from 2 to 20 of terpenic structural units, preferably from 2 to 10 terpenic structural units, and more preferably 2 to 5 terpenic structural units.

[0050] A terpenic structural units correspond to any terpene derived from hydrocarbon isoprene (CsHs)n with n a number ranging from 2 to 8, preferably 2 to 4, and more preferably 2.

[0051] Non limiting examples of terpenic structural units may include alpha pinene, beta pinene, dipentene, beta phellandrene, alpha phellandrene and mixture thereof. Preferably, the terpenic structural units are alpha pinene, beta pinene or a mixture thereof.

[0052] Terpenic oligomer can typically be obtained, from a plant such as tree and typically from conifers, in particular from pine trees, as a based oil. Terpenic oligomer can be a based oil such as a citrus oil. The citrus oil may be selected from the group consisting of orange oil, lemon oil, lime oil, grapefruit oil, and tangerine oil. Alternatively, the terpenic oligomer may be obtained by polymerization of a terpene or a mixture of terpenes. Terpenes can be extracted from tapping industry by first tapping live trees, collecting oleoresin with a final distillation of the gum obtained to separate the gum turpentine (GT) from the gum rosin. GT is typically a highly concentrated sulfur-free mixture of non-oxygenated monoterpenes. Alternatively, the terpenes may be recovered from the kraft pulping industry wherein terpenic compounds are extracted as a stream from the wood pulp and named Crude Sulfate. Alternatively, the terpenes may be extracted from materials that are harvested from pine tree, particularly from pine tree stumps, for example through solvent extraction and / or distillation.

[0053] None limitative examples of trees used for tapping, kraft pulping industry or harvesting are Araucaria; Cedar (Cedrus); Cypress (Chamaecyparis, Cupressus, Taxodium); Rocky Mountain Douglas-fir (Pseudotsuga menziesii var. glauca); European Yew (Taxus baccata); Fir (Abies); Hemlock (Tsuga): Eastern Hemlock (Tsuga canadensis), Mountain Hemlock (Tsuga mertensiana), Western Hemlock (Tsuga heterophylla); Kauri (New Zealand) (Agathis australis); Kaya (Torreya nucifera); Larch (Larix); Pine (Pinus); Spruce (Picea); Whitecedar and Yellowcedar (Nootka Cypress Callitropsis nootkatensis, formerly Chamaecyparis nootkatensis); Redcedar; Redwood (Sequoia sempervirens) and Rimu (New Zealand) (Dacrydium cupressinum).

[0054] Typically the Cypress (Chamaecyparis, Cupressus, Taxodium) is selected from Arizona Cypress (Cupressus arizonica), Bald Cypress or Southern cypress (Taxodium distichum), Hinoki Cypress (Chamaecyparis obtusa), Lawson's Cypress (Chamaecyparis lawsoniana) and Mediterranean Cypress (Cupressus sempervirens).

[0055] Typically the Hemlock (Tsuga) is selected from, Eastern Hemlock (Tsuga canadensis), Mountain Hemlock (Tsuga mertensiana) and Western Hemlock (Tsuga heterophylla)

[0056] Typically the Larch (Larix) is selected from, European Larch (Larix decidua), Japanese Larch (Larix kaempferi), Tamarack Larch or Tamarack (Larix laricina), Western Larch (Larix occidentalis)

[0057] Typically the Pine (Pinus) is selected from, Corsican pine (Pinus nigra), Jack Pine (Pinus banksiana), Lodgepole Pine (Pinus contorta subsp latifolia), Monterey Pine (Pinus radiata), Ponderosa Pine (Pinus ponderosa), Red Pine (N.Am.) (Pinus resinosa), Scots Pine, Red pine (UK), Red deal (UK), Redwood (UK, obsolete) (Pinus sylvestris), White Pine (Yellow or Weymouth pine, Eastern White Pine (Pinus strobus), Western White Pine (Pinus monticola), Sugar Pine (Pinus lambertiana)), Southern Yellow pine (Loblolly Pine (Pinus taeda), Longleaf Pine (Pinus palustris), Pitch Pine (Pinus rigida), Shortleaf Pine (Pinus echinata)), Maritime pine (Pinus Pinaster), Pinus el liottii - Slash pine (Pinus El liottii), Masson's pine (Pinus Massoniana), Aleppo pine (Pinus Halepensis) Sumatra Pine (Pinus Merkusii) and Monterey pine, radiata pine (Pinus Radiata).

[0058] Tree of particular interest are more specifically Maritime pine (Pinus Pinaster), Pinus el liottii - Slash pine (Pinus Elliottii), Masson's pine (Pinus Massoniana), Aleppo pine (Pinus Halepensis) and Monterey pine, radiata pine (Pinus Radiata).

[0059] Typically the Spruce (Picea) is selected from Norway Spruce (Picea abies), Black Spruce (Picea mariana), Red Spruce (Picea rubens), Sitka Spruce (Picea sitchensis), White Spruce (Picea glauca) and Sugi (Cryptomeria japonica).

[0060] Typically the Whitecedar is selected from Northern Whitecedar (Thuja occidentalis), Southern Whitecedar (Chamaecyparis thyoides).

[0061] Typically the Redcedar is selected from Eastern Redcedar, (Juniperus virginiana), Western redcedar (Thuja plicata)

[0062] Typically the Araucaria is selected from, Hoop Pine (Araucaria cunninghamii); Parana Pine (Araucaria angustifolia); Pehuen or Chile Pine (Araucaria araucana);

[0063] Typically the Cypress (Chamaecyparis, Cupressus, Taxodium) is selected from, Arizona Cypress (Cupressus arizonica), Bald Cypress or Southern cypress (Taxodium distichum), Hinoki Cypress (Chamaecyparis obtusa), Lawson's Cypress (Chamaecyparis lawsoniana), Mediterranean Cypress (Cupressus sempervirens). In a preferred embodiment the terpenic oligmer is a molecule terpenic oligomer is a molecule containing from 2 to 20 of terpenic structural units, more preferably 2 to 10 terpenic structural units, wherein the terpenic structural units correspond to any terpene derived from hydrocarbon isoprene (CsHs)n with n a number ranging from 2 to 8 and which is not further functionalized by any heteroatomic groups, such as hydroxy groups, amine groups or sulfur groups.

[0064] In a preferred embodiment, the terpenic oligomer is an oligomer of pinene, more preferably an oligomer of alpha-pinene and beta-pinene.

[0065] In a preferred embodiment, the terpenic oligomer is Derphalin® obtained from pine extraction and produced by DRT, and registered under Reach regulation with CAS n°70750-57-l.

[0066] Terpenic oligomers can be a mixture containing at least 50 wt % of terpenic oligomer, typically as a mixture of oligomers, preferably from 50 to 99 wt. %with respect to the total weight of the extract. Typically, terpenic oligomers are a mixture when obtained from plant.

[0067] Advantageously, terpenic oligomers of the invention are sticker and penetrant agents and improve the spray retention when used in a spraying composition.

[0068] According to the invention, the co-formulation composition comprises a terpenic alcohol.

[0069] The term "terpenic alcohol" will be understood by a person of ordinary skill in the art as encompassing primary, secondary, and tertiary alcohol derivatives of terpenes. Non-limiting examples of terpene alcohols include terpineol (e.g., a-terpineol), linalool, borneol, geraniol, menthol, citronellol, nerol, and nopol. In some embodiments, the terpene alcohol may be a synthetic terpene alcohol, for example, ethanol, 2-[[2-[(lR)-4-methyl-3-cyclohexen-l- yl]propyl]thio] (CAS number: 1329428-49-0) and 3-cyclohexene-l-propanol, 4-methyl-y- methylene- (CAS number: 15766-66-2).

[0070] In some embodiments, terpenic alcohol is obtained from plant such as a citrus oils or pine terpenes, preferably as a cut containing terpenic alcohol(s). Preferably, the amount of terpenic alcohol(s) in a cut obtained from plant is greater than 50 wt. %, typically as a mixture of different alcohols, preferably from 50 to 99 wt. %, more preferably from 80 to 95 wt. % with respect to the total weight of the cut. Typically, terpenic alcohol(s) can be a mixture of terpenic alcohol when obtained from plant such as a mixture of terpineol isomers, i.e. alpha terpineol, beta terpineol, gamma terpineol, delt terpineol, terpinene-4-ol. Preferably, the terpenic alcohol is selected from the group consisting of 2,6-dimethyloct-7-en- 2-ol, 4(8)-p-menthen-l-ol, cis-3,7-dimethyl-2,6-octadien-8-ol, trans-3,7-dimethyl-2,6- octadien-l-ol,10-hydroxymethylene-2-pinene, 3,7-dimethyloct-6-en-l-ol and terpineol isomers such as alpha terpineol, beta terpineol, gamma terpineol, delt terpineol, terpinene-4- ol and a mixture thereof.

[0071] Advantageously, terpenic alcohols of the invention are wetting agent and improve the spreading when used in a composition.

[0072] The co-formulation composition has, typically, a weight ratio of terpenic alcohol to terpenic oligomer ranging from 0.5 to 8, preferably from 0.8 to 6, preferably from 1 to 4, and more preferably from 1.2 to 2.5.

[0073] In a preferred embodiment, the co-formulation composition, is an artificial co-formulation composition. Thereby, it is understood that the co-formulation is formulated by combining a terpenic oligomer and terpenic alcohol which are not combined in a natural composition such as an essential oil.

[0074] In a preferred embodiment, the co-formulation composition is a co-formulation which is not an essential oil.

[0075] A phytosanitary and / or biostimulant composition

[0076] One other aspect of the invention concerns a phytosanitary and / or biostimulant composition comprising the co-formulation composition of terpenic oligomer and terpenic alcohol as described above, one or more phytosanitary and / or biostimulant active substance(s) and optionally any other ingredients, typically for plant treatment. The other ingredients are selected in function of the used of the phytosanitary and / or biostimulant composition in accordance with the skilled person general knowledge.

[0077] When used in a phytosanitary and / or biostimulant composition, typically for plant treatment, the co-formulation composition of terpenic oligomers and terpenic alcohol has one or more of the following advantages:

[0078] - improvement of spray retention explained by sticker effect, and / or

[0079] - improvement of rainfastness, and / or

[0080] - increasing active substance penetration in plant, and / or

[0081] - delay of droplet drying, and / or

[0082] - preservation against UV photodegradation, and / or

[0083] - drift reduction, and / or

[0084] - efficacy improvement of plant protection at a reduced rate and / or

[0085] - reducing the phytotoxicity of an active substance; and / or

[0086] - enhancing the selectivity of an active substance.

[0087] The composition of the invention allows reductions of pollution and of active substance rate. Without wishing to be bound by theory, the terpenic oligomer polymerize with UV and heat when drying after application which stabilize the phytosanitary and / or biostimulant composition.

[0088] Further without wishing to be bound by theory, there is also a siccativation, i.e. oxidation reaction with of the unsaturation of the polymers in the presence of oxygen from the air after application which also participate to stabilize the phytosanitary and / or biostimulant composition.

[0089] The composition comprises typically from 1 to 10 wt. % of terpenic oligomer, preferably from 2 to 8 wt. % of terpenic oligomer and more preferably from 3 to 6 wt. % of terpenic oligomer with respect to the total weight of composition.

[0090] The composition comprises typically from 1 to 10 wt. % of terpenic alcohol, preferably from 2 to 8 wt. % of terpenic alcohol and more preferably from 3 to 6 wt. % of terpenic alcohol with respect to the total weight of composition.

[0091] Active substance(s)

[0092] The phytosanitary and / or biostimulant active substance can be selected from the group consisting of insecticide, bactericide, fungicide, insect repellent or attractant and mixtures thereof.

[0093] A phytosanitary product, plant protection product or phytopharmaceutical is a substance or a mixture of substances of chemical or biological nature (of natural or synthetic origin) used in agriculture, horticulture or forestry to protect cultivated plants against bio-aggressors (animal pests, phytopathogenic agents, parasitic plants, weeds) or to optimize crops by promoting the growth of cultivated plants and by treating their environment (in particular the soil).

[0094] Biostimulant means a substance that stimulates plant nutritional processes independently of the nutrients it contains with the aim of improving one or more of the following characteristics of plants or their rhizosphere: nutrient use efficiency, abiotic stress tolerance, quality characteristics, availability of nutrients confined in the soil or rhizosphere (according to EU Regulation 2019 / 1009).

[0095] Biostimulants can be certain natural preparations of little concern. They are:

[0096] - Either natural substances for biostimulant use; or

[0097] - basic substances.

[0098] The basic substances are defined by Article 23 of Regulation (EC) 1107 / 2009. They are substances with phytosanitary interest but whose main use is other than plant protection (e.i. foodstuffs). The composition comprises typically from 10 to 70 wt. % of active substance(s), preferably from 30 to 65 wt. % of active substance(s) and more preferably from 50 to 60 wt. % of active substance(s) with respect to the total weight of composition.

[0099] The active substance can be a fungicide, insecticide, and other chemicals which are used to control fungi, nematodes, mites, insects, rodents and other animals and plants or viruses (to be referred to as "pests") that damage agricultural crops that include trees and forestry products, to be collectively referred to as "agricultural crops", and plant growth regulator, germination inhibitor or other chemical used to enhance or inhibit the physiological functions of agricultural crops. There are no particular limitations on the chemical used for agriculture, any chemical can be used, and may be any of an insecticide, fungicide or herbicide. Preferably, the active substance is selected from the group of all approved active substances are listed in Implementing Regulation of European Union No 540 / 2011, in the list Pesticides Database of European Union, and a mixture thereof.

[0100] Typically, the active substance is a biocontrol active substance, preferably selected from the group consisting of insecticide, bactericide, fungicide, insect repellent or attractant and mixtures thereof.

[0101] Preferably, the active substance can be selected from the group consisting of sulfur, copper such as copper hydroxide, copper sulfate, copper oxychloride, pelargonic acid, orange essential oil and a mixture thereof. Typically, the sulfur has the CAS number 7704-34-9, preferably the sulfur is in a micronized form.

[0102] For example, a herbicide can be selected from the group consisting of pelargonic acid, allyloxy propionate inhibitors of acetyl CoA carboxylase (ACCase), cyclohexanedione inhibitors of acetyl CoA carboxylase (ACCase), phenylpyrazoline inhibitors of acetyl CoA carboxylase (ACCase), sulfonylurea inhibitors of acetolactic acid synthase (ALS) (acetohydroxy acid synthase (AHAS) inhibitors), imidazolinone inhibitors of acetolactic acid synthase (ALS) (acetohydroxy acid synthase (AHAS) inhibitors), triazolopyrimidine inhibitors of acetolactic acid synthase (ALS) (acetohydroxy acid synthase (AHAS) inhibitors), pyrimidinyl(thio)benzoate inhibitors of acetolactic acid synthase (ALS) (acetohydroxy acid synthase (AHAS) inhibitors), sulfonylaminocarbonyl-triazolinone inhibitors of acetolactic acid synthase (ALS) (acetohydroxy acid synthase (AHAS) inhibitors), triazine inhibitors of photosynthesis at photochemical system II, triazinone inhibitors of photosynthesis at photochemical system II, triazolinone inhibitors of photosynthesis at photochemical system II, uracil inhibitors of photosynthesis at photochemical system II, pyridazinone inhibitors of photosynthesis at photochemical system II, phenyl-carbamate inhibitors of photosynthesis at photochemical system II, urea inhibitors of photosynthesis at photochemical system II, amide inhibitors of photosynthesis at photochemical system II, nitrile inhibitors of photosynthesis at photochemical system II, benzothiadiazinone inhibitors of photosynthesis at photochemical system II, phenyl-pyridazine inhibitors of photosynthesis at photochemical system II, bipyridylium photochemical system I electron diverting agents, diphenylether inhibitors of protoporphyrinogen oxidase (PPO), phenylpyrazole inhibitors of protoporphyrinogen oxidase (PPO), N-phenylphthalimide inhibitors of protoporphyrinogen oxidase (PPO), thiadiazole inhibitors of protoporphyrinogen oxidase (PPO), oxadiazole inhibitors of protoporphyrinogen oxidase (PPO), triazolinone inhibitors of protoporphyrinogen oxidase (PPO), oxazolidinedione inhibitors of protoporphyrinogen oxidase (PPO), pyrimidindione inhibitors of protoporphyrinogen oxidase (PPO), inhibitors of protoporphyrinogen oxidase (PPO), pyridazinone inhibitors of carotenoid biosynthesis at the phytoene desaturase step (PDS), pyridinecarboxamide inhibitors of carotenoid biosynthesis at the phytoene desaturase step (PDS), inhibitors of carotenoid biosynthesis at the phytoene desaturase step (PDS), triketone inhibitors of 4-hydroxyphenyl-pyruvate-dioxygenase (4-HPPD), isoxazole inhibitors of 4- hydroxyphenyl-pyruvate-dioxygenase (4-HPPD), pyrazole inhibitors of 4-hydroxyphenyl- pyruvate-dioxygenase (4-HPPD), inhibitors of 4-hydroxyphenyl-pyruvate-dioxygenase (4- HPPD), triazole inhibitors of carotenoid biosynthesis , isoxazolidinone inhibitors of carotenoid biosynthesis, urea inhibitors of carotenoid biosynthesis, diphenylether inhibitors of carotenoid biosynthesis glycine inhibitors of EPSP synthase, phosphinic acid inhibitors of glutamine synthetase, carbamate inhibitors of DHP (dihydropteroate) synthase, dinitroaniline microtubule assembly inhibitors, phosphoramidate microtubule assembly inhibitors, pyridine microtubule assembly inhibitors, benzamide microtubule assembly inhibitors, benzoic acid microtubule assembly inhibitors, carbamate inhibitors of mitosis / microtubule organisation, chloroacetamide inhibitors of VLCFAs (inhibitors of cell division), acetamide inhibitors of VLCFAs (inhibitors of cell division), oxyacetamide inhibitors of VLCFAs (inhibitors of cell division), tetrazolinone inhibitors of VLCFAs (inhibitors of cell division), inhibitors of VLCFAs (inhibitors of cell division), nitrile inhibitors of cell wall (cellulose) synthesis, benzamide inhibitors of cell wall (cellulose) synthesis, triazolocarboxamide inhibitors of cell wall (cellulose) synthesis, quinoline carboxylic acid inhibitors of cell wall (cellulose) synthesis, dinitrophenol uncoupling (membrane disruption) agents, thiocarbamate inhibitors of lipid synthesis (non-ACCase inhibitors), phosphorodithioate inhibitors of lipid synthesis (non- ACCase inhibitors), benzofuran inhibitors of lipid synthesis (non-ACCase inhibitors), chloro- carbonic-acid inhibitors of lipid synthesis (non-ACCase inhibitors), phenoxy-carboxylic-acid indole acetic acid-like agents (synthetic auxins), benzoic acid indole acetic acid-like agents (synthetic auxins), pyridine carboxylic acid indole acetic acid-like agents (synthetic auxins), quinoline carboxylic acid indole acetic acid-like agents (synthetic auxins), indole acetic acidlike agents (synthetic auxins), phthalamate inhibitors of auxin transport, semicarbazone inhibitors of auxin transport, arylaminopropionic acids, pyrazoliums, organoarsenicals, microorganisms, bromobutide, (chlor)-flurenol, cinmethylin, cumyluron, dazomet, dymron, methyl dymron, etobenzanid, fosamine, indanofan, carbam / carbam sodium salt, oxaziclomefone, oleic acid, pelargonic acid, pyributicarb, chlorates and cyanates, and a mixture thereof. For example, an insecticide can be selected from the group consisting of orange essential oil, carbamate acetylcholinesterase (AChE) inhibitors, organophosphorous acetylcholinesterase (AChE) inhibitors, phenylpyrazole (fiprole) GABA-gated chlorine ion channel blockers, pyrethroid and pyrethrin sodium channel modulators, sodium channel modulators, neonicotinoid nicotinic acetylcholine receptor (nAChR) competitive modulators, sulfoximine nicotinic acetylcholine receptor (nAChR) competitive modulators, spinosyn nicotinic acetylcholine receptor (nAChR) allosteric modulators, avermectin and milbemycin glutamate- gated chloride channel (GluCI) allosteric modulators, chordotonal organ TRPV channel modulators, uncouplers of oxidative phosphorylation via disruption of the proton gradient, mitochondrial complex III electron transport inhibitors, mitochondrial complex I electron transport inhibitors, voltage-dependent sodium channel blockers, tetronic acid and tetramic acid derivative inhibitors of acetyl CoA carboxylase, diamide ryanodine receptor modulators, flonicamid chordotonal organ modulators, quinoxaline (quinomethionate), pyridalyl and metaldehyde, and a mixture thereof.

[0103] For example, a fungicide can be selected from the group consisting of sulfur, copper such as copper hydroxide, copper sulfate, copper oxychloride, acylanaline PA fungicides (phenylamides), oxazolidinone PA fungicides (phenylamides), butyrolactone PA fungicides (phenylamides), isoxazole heteroaromatics, benzimidazole MBC fungicides (methyl benzimidazole carbamate), N-phenyl carbamates, phenyl-benzamide SDHI (succinate dehydrogenase inhibitors), phenyl-oxo-ethyl thiophene amide SDHI (succinate dehydrogenase inhibitors), pyridinyl-ethyl-benzamide SDHI (succinate dehydrogenase inhibitors), furan-carboxamide SDHI (succinate dehydrogenase inhibitors), oxathiin- carboxamide SDHI (succinate dehydrogenase inhibitors), thiazole-carboxamide SDHI (succinate dehydrogenase inhibitors), pyrazole-4-carboxamide SDHI (succinate dehydrogenase inhibitors), N-methoxy-(phenyl-ethyl)-pyrazole-carboxamide SDHI (succinate dehydrogenase inhibitors), pyridine-carboxamide SDHI (succinate dehydrogenase inhibitors), methoxy-acrylate Qol-fungicides (Quinone outside inhibitors), methoxy-acetamide Qol- fungicides (Quinone outside inhibitors), methoxy-carbamate Qol-fungicides (Quinone outside inhibitors), oximino-acetate Qol-fungicides (Quinone outside inhibitors), oximino-acetamide Qol-fungicides (Quinone outside inhibitors), oxazolidine-dione Qol-fungicides (Quinone outside inhibitors), dihydro-dioxazine Qol-fungicides (Quinone outside inhibitors), imidazolinone Qol-fungicides (Quinone outside inhibitors), benzyl-carbamate Qol-fungicides (Quinone outside inhibitors), cyano-imidazole Qil-fungicides (Quinone inside inhibitors), sulfamoyl-triazole Qil-fungicides (Quinone inside inhibitors), 2,6-dinitroanilines, anilino- pyrimidine AP-fungicides (aniline-pyrimidines), phenylpyrrole PP-fungicides (phenylpyrroles), dicarboximides, piperazine DMI-fungicides (demethylation inhibitors, SBI: class I), pyridine DMI-fungicides (demethylation inhibitors, SBI: class I), pyrimidine DMI-fungicides (demethylation inhibitors, SBI: class I), imidazole DMI-fungicides (demethylation inhibitors, SBI: class I), triazole DMI-fungicides (demethylation inhibitors, SBI: class I), triazolinethione DMI-fungicides (demethylation inhibitors, SBI: class I), isobenzo-furanone MBI-R (melanin biosynthesis inhibitors-reductase), pyrrolo-quinolinone MBI-R (melanin biosynthesis inhibitors-reductase), triazolobenzo-thiazole MBI-R (melanin biosynthesis inhibitors- reductase), cyclopropane-carboxamide MBI-D (melanin biosynthesis inhibitors-dehydratase), carboxamide MBI-D (melanin biosynthesis inhibitors-dehydratase), propionamide MBI-D (melanin biosynthesis inhibitors-dehydratase), benzo-thiadiazoles BTH, benzisothiazoles, thiadiazole-carboxamides, cyanoacetamide-oximes, benzene-sulfonamides, pyridazinones, guanidines and quinoxalines, and a mixture thereof.

[0104] Other ingredients

[0105] The phytosanitary and / or biostimulant composition can also comprise one or more ingredients selected from the group consisting of a surfactant anionic or not, a polyol, glycerol, an anti-foam agent, a pH regulator and a mixture thereof.

[0106] The phytosanitary and / or biostimulant composition can comprise an anionic surfactants, preferably selected from the group consisting of sulfonates; sulfates; sulfosuccinates; sarcosinates; alcohol sulfates; alcohol ether sulfates; alkylaryl ether sulfates; alkylaryl sulfonates such as alkylbenzene sulfonates and alkylnaphthalene sulfonates and salts thereof; alkyl sulfonates; mono- or di-phosphate esters of polyalkoxylated alkyl alcohols or alkylphenols; mono- or di-sulfosuccinate esters of C12-C15 alkanols or polyalkoxylated C12- C15 alkanols; ether carboxylates, especially alcohol ether carboxylates; phenolic ether carboxylates; polybasic acid esters of ethoxylated polyoxyalkylene glycols consisting of oxybutylene or the residue of tetrahydrofuran; sulfoalkylamides and salts thereof such as N- methyl-N-oleoyltaurate Na salt; polyoxyalkylene alkylphenol carboxylates; polyoxyalkylene alcohol carboxylates alkyl polyglycoside / alkenyl succinic anhydride condensation products; alkyl ester sulfates; naphthalene sulfonates; naphthalene formaldehyde condensates; alkyl sulfonamides; sulfonated aliphatic polyesters; sulfate esters of styrylphenyl alkoxylates; and sulfonate esters of styrylphenyl alkoxylates and their corresponding sodium, potassium, calcium, magnesium, zinc, ammonium, alkylammonium, diethanolammonium, or triethanolammonium salts; salts of ligninsulfonic acid such as the sodium, potassium, magnesium, calcium or ammonium salt; polyarylphenol polyalkoxyether sulfates and polyarylphenol polyalkoxyether phosphates; and sulfated alkyl phenol ethoxylates and phosphated alkyl phenol ethoxylates; sodium lauryl sulfate; sodium laureth sulfate; ammonium lauryl sulfate; ammonium laureth sulfate; sodium methyl cocoyl taurate; sodium lauroyl sarcosinate; sodium cocoyl sarcosinate; potassium coco hydrolyzed collagen; TEA (triethanolamine) lauryl sulfate; TEA (Triethanolamine) laureth sulfate; lauryl or cocoyl sarcosine; disodium oleamide sulfosuccinate; disodium laureth sulfosuccinate; disodium dioctyl sulfosuccinate; N-methyl-N-oleoyltaurate Na salt; tristyrylphenol sulphate; ethoxylated lignin sulfonate; ethoxylated nonylphenol phosphate ester; calcium alkylbenzene sulfonate; ethoxylated tridecylalcohol phosphate ester; dialkyl sulfosuccinates; perfluoro (C6- C18)alkyl phosphonic acids; perfluoro(C6-C18)alkyl-phosphinic acids; perfluoro(C3-C20)alkyl esters of carboxylic acids; alkenyl succinic acid diglucamides; alkenyl succinic acid alkoxylates; sodium dialkyl sulfosuccinates; and alkenyl succinic acid alkylpolyglykosides. Further exemplification of suitable anionic emulsifiers include, but are not limited to, water-soluble salts of alkyl sulfates, alkyl ether sulfates, alkyl isothionates, alkyl carboxylates, alkyl sulfosuccinates, alkyl succinamates, alkyl sulfate salts such as sodium dodecyl sulfate, alkyl sarcosinates, alkyl derivatives of protein hydrolyzates, acyl aspartates, alkyl or alkyl ether or alkylaryl ether phosphate esters, sodium dodecyl sulphate, phospholipids or lecithin, or soaps, sodium, potassium or ammonium stearate, oleate or palmitate, alkylarylsulfonic acid salts such as sodium dodecylbenzenesulfonate, sodium dialkylsulfosuccinates, dioctyl sulfosuccinate, sodium dilaurylsulfosuccinate, polystyrene sulfonate) sodium salt, alkylenemaleic anhydride copolymers such as isobutylene-maleic anhydride copolymer, or ethylene maleic anhydride copolymer gum arabic, sodium alginate, carboxymethylcellulose, cellulose sulfate and pectin, polystyrene sulfonate), pectic acid, tragacanth gum, almond gum and agar; semi-synthetic polymers such as carboxymethyl cellulose, sulfated cellulose, sulfated methylcellulose, carboxymethyl starch, phosphated starch, lignin sulfonic acid; maleic anhydride copolymers (including hydrolyzates thereof), polyacrylic acid, polymethacrylic acid, acrylic acid alkyl acrylate copolymers such as acrylic acid butyl acrylate copolymer or crotonic acid homopolymers and copolymers, vinylbenzenesulfonic acid or 2-acrylamido-2- methylpropanesulfonic acid homopolymers and copolymers, and partial amide or partial ester of such polymers and copolymers, carboxymodified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol and phosphoric acid-modified polyvinyl alcohol, phosphated or sulfated tristyrylphenol ethoxylates. Preferably, the anionic surfactant is selected from the group consisting of phosphated tristyrylphenol ethoxylates, sodium salt of naphthalene sulfonate and a mixture thereof.

[0107] The composition comprises typically from 0.5 to 4 wt. % of anionic surfactant, preferably from 1 to 3 wt. % and more preferably from 1.5 to 2.5 wt. % of anionic surfactant with respect to the total weight of composition.

[0108] The phytosanitary and / or biostimulant composition can comprise non-ionic surfactants, preferably instead of anionic surfactant. The non-ionic surfactants can be selected from the group consisting of acrylic polymer, alkyl polyglucoside, polyoxyethylene sorbitan esters, polyoxypropylene sorbitan esters, ethoxylated castor oil, ethoxylated fatty alcohol, glycereth- 2-cocoate (levenol), ethoxylated amine, ethoxylated tristyrylphenol and a mixture thereof.

[0109] The composition comprises typically from 1 to 20 wt.%, preferably from 2 to 15 wt.%, and more preferably 5 to 10 wt.% of non-ionic surfactants with respect to the total weight of composition.

[0110] The phytosanitary and / or biostimulant composition can comprise polyol, preferably selected from the group consisting of propylene glycol, glycerol and a mixture thereof. The composition comprises typically from 0.5 to 10 wt. % of polyol, preferably from 1 to 5 wt. % and more preferably from 2 to 4 wt. % of polyol with respect to the total weight of composition.

[0111] In a preferred embodiment, the composition comprises from 2 to 4 wt. % of polyol, preferably of propylene glycol and from 1 to 3 wt. % of glycerol.

[0112] Preferably, the phytosanitary and / or biostimulant composition can comprise glycerol (also called glycerin). The composition comprises typically from 0.5 to 10 wt. % of glycerol, preferably from 1 to 5 wt. % and more preferably from 1 to 3 wt. % of glycerol with respect to the total weight of composition.

[0113] Typically, the phytosanitary and / or biostimulant composition can comprise, preferably for the stability of the composition, an anti-foam agent such as a silicone emulsion, fatty acid alkoxylate, alcohol alkoxylate, carboxylic acid ester, phosphoric ester, alkypolyalkylene glycol ether. The composition comprises typically from 0.001 to 1 wt. % of anti-foam agent, preferably from 0.002 to 0.02 wt. % and more preferably from 0.005 to 0.015 wt. % of antifoam agent with respect to the total weight of composition.

[0114] Typically, the phytosanitary and / or biostimulant composition can comprise, preferably for the stability of the composition, a thickener agent such as gum xanthan, guar gum, polyacrylate, polycarboxylate, cellulose ether, silica derivates. The composition comprises typically from 1 to 20 wt. % of anti-foam agent, preferably from 5 to 15 wt. % and more preferably from 8 to 12 wt. % of anti-foam agent with respect to the total weight of composition.

[0115] Typically, the phytosanitary and / or biostimulant composition can comprise, preferably for the stability of the composition, an anti-foam agent such as a silicone emulsion. The composition comprises typically from 0.01 to 1 wt. % of anti-foam agent, preferably from 0.02 to 0.5 wt. % and more preferably from 0.025 to 0.1 wt. % of anti-foam agent with respect to the total weight of composition.

[0116] The phytosanitary and / or biostimulant composition can comprise a pH regulator. Advantageously, the pH of the composition is adjusted in function of the type of plant treatment for which the phytosanitary and / or biostimulant composition is directed. For example, the pH can range from 7 to 10, preferably from 8 to 9. The pH can be adjusted by addition of a pH regulator. Preferably, the pH regulator is selected from the group consisting in sodium hydroxide, potassium hydroxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, and more preferably potassium hydroxide. The composition comprises typically from 0.1 to 1 wt. % of pH regulator, preferably from 0.15 to 0.8 wt. % and more preferably from 0.2 to 0.5 wt. % of pH regulator with respect to the total weight of composition. In some embodiment, the phytosanitary and / or biostimulant composition can comprise also water. The composition contains a quantity of water sufficient to reach a total amount of 100 wt. %.

[0117] A preferred phytosanitary and / or biostimulant composition comprises, preferably consists of, terpenic alcohol from 1 to 10 wt. %, preferably of 2,6-dimethyloct-7-en-2-ol; terpenic oligomer from 1 to 10 wt. %, preferably Derphalin®; active substance from 20 to 70 wt. %, preferably selected from the group consisting of sulfur, copper such as copper hydroxide, copper sulfate, copper oxychloride, pelargonic acid, orange essential oil and a mixture thereof; and eventually one or more of ingredients selected from the group consisting of: anionic surfactant from 1 to 2 wt. %, preferably tristyrylphenol anionic; and / or polyol from 1 to 5 wt. %, preferably propylene glycol; and / or non-ionic surfactants from 1 to 20 wt.%, and / or glycerol from 1 to 5 wt. %, preferably from 2 to 4 wt. % of propylene glycol and from 1 to 3 wt. % of glycerol; and / or anti-foam agent from 0.01 to 1 wt. %, a silicon emulsion; and / or pH regulator from 0.1 to 1 wt.%, preferably sodium hydroxide; and / or and a mixture thereof; water qsp 100 wt. %; the % are expressed in respect to the total weight of composition.

[0118] The composition contains a quantity of water sufficient to reach a total amount of 100 wt. %, abbreviated "qsp".

[0119] The phytosanitary and / or biostimulant composition described above can be formulated according to any method known from the skilled person in the art. The composition can be formulated in the form of a liquid, a suspension, an emulsion, a concentrated emulsion, a dispersion, a suspoemulsion, an emulsifiable concentrate or slurry of particles in an aqueous medium. Advantageously, the composition is formulated as an oil-based dispersion, concentrated emulsion, an emulsifiable concentrate, an emulsion or a suspoemulsion, preferably in an aqueous solution. Typically, the emulsion is formulated with a hydrophilic phase, a lipophilic phase and one or more surfactant. The surfactant binds the two immiscible phases together.

[0120] Preferably, the composition is formulated in the form of a suspoemulsion or an oil-based dispersion for solid active substance(s) such as sulfur or copper.

[0121] Preferably, the composition is formulated in the form of a concentrated emulsion or an emulsifiable concentrate for liquid active substance(s). Methods of preparation

[0122] One aspect of the invention is directed to a method of preparation of the co-formulation for the composition as described above.

[0123] The method of preparation of the co-formulation comprises a step of mixing a solution of the terpenic oligomer with a solution of the terpenic alcohol.

[0124] The present invention is also directed to a preparation of a phytosanitary and / or biostimulant composition comprising the co-formulation. Advantageously, the preparation of the composition comprises a step of mixing a solution of the terpenic oligomer with a solution of the terpenic alcohol.

[0125] The solution of terpenic alcohol can be prepared by a method comprising a step of mixing terpenic alcohol with one or more active substance(s), water and eventually one or more other ingredients selected from the group consisting of a surfactant anionic or not, a polyol, glycerol, and anti-foam agent, a pH regulator and a mixture thereof as described above.

[0126] The method of preparing the solution of terpenic alcohol can further comprise a step of milling to obtain the desired particle size of active substance.

[0127] The solution of terpenic alcohol prepared by the method above is then mixed with terpenic oligomer, eventually water, and eventually a thickener preferably in solution in water.

[0128] In a preferred embodiment, the method of preparation of the composition comprises a step (i) of mixing terpenic alcohol as defined above with at least anionic surfactant as defined above; a step (ii) of adding one or more active substance(s) as defined above; a step (iii) of milling to obtain the desired particle size of active substance; a step (iv) of adding the terpenic oligomers as defined above; a step (v) of eventually adding a thickener as defined above, preferably in solution in water; a step (vi) of mixing in order to obtain the composition eventually a step (vii) of adjustment of the physico-chemical characteristics of the composition, preferably to guarantee stability.

[0129] Preferably, the composition is a suspension without lumps.

[0130] The composition obtained with the method above has, advantageously, the following physico-chemical characteristics:

[0131] - A pH at 20°C ranging from 7 to 9; and / or

[0132] - A density at 20°C ranging from 1.41 to 1.43 g / ml; and / or

[0133] - A viscosity Ford cup 4 at 20°C ranging from 60 to 80.

[0134] The composition can be a dispersion, preferably at 3 vol. % in water with the following characteristics:

[0135] Suspensibility (ml sediment) ranging from 0 to 0.5; and / or

[0136] Foaming (cm) ranging from 0 to 1.5 The invention concerns also a method of preparation of a phytosanitary and / or biostimulantcomposition described above. The method of preparation of the phytosanitary and / or biostimulant composition can be as described above.

[0137] Preferably, at step (i) can also be added one or more of water, a pH regulator, glycerol, propylene glycol, dispersing agent. Step (i) is preferably performed under stirring at room temperature.

[0138] Preferably, at step (ii) can also be added an anti-foam as described above.

[0139] Preferably, all steps are performed under stirring, preferably at room temperature.

[0140] Preferably, the milling is performed with DYNO-MILL to the desired particle size. For example, when the active substance is sulfur, then the granulometry is as follows:

[0141] - Median diameter (pm) ranging from 0 to 3.2;

[0142] - Refusal passing 90% (pm) ranging from 0 to 8;

[0143] - Reject sieve 75 pm (%) ranging from 0 to 0.1;

[0144] - Reject sieve 100 pm (%) ranging from 0 to 0.

[0145] Uses

[0146] The present invention concerns also the use of a co-formulation composition as described above for preparing a phytosanitary and / or biostimulant composition, preferably for plant treatment. Preferably, the co-formulation composition as described above improves:

[0147] - spray retention explained by sticker effect; and / or

[0148] - rainfastness; and / or

[0149] - active substance penetration in plant; and / or

[0150] - delay of droplet drying; and / or

[0151] - preservation against UV photodegradation; and / or

[0152] - drift reduction of one or more phytosanitary and / or biostimulant active substance(s).

[0153] Another aspect of the present invention relates to a method of treating plant such as tree or crops by application of a phytosanitary and / or biostimulant composition described above. Preferably, the composition is sprayed.

[0154] Advantageously, the phytosanitary and / or biostimulant composition of the invention allows to reduce the amount of active substance(s) rate from 25 to 50% for the treatment of crops or plant. EXAMPLES

[0155] The following examples illustrate the invention without limiting it.

[0156] Method Phytotoxicity is a physiological damage that a chemical substance can cause on the cultivated plant. It is controlled during the whole period of the test and until the harvest during the various notations, observations, and applications of pulverizations. Symptoms of phytotoxicity can be manifested by leaf speckling, necrosis (browning) or chlorosis (yellowing) of the leaf margins, brown or yellow spots or patches on the leaves, leaf curling or twisting. A rating of the percentage of damaged leaves is used to assess phytotoxicity based on a visual evaluation.

[0157] Granulometry is determined by sieving of the sulfur particles and a laser granulometer.

[0158] Materials:

[0159] The following table describes materials used to prepare a phytosanitary composition used in the examples below:

[0160] Table 1

[0161] Derphalin® is a terpenic oligomers mixture extracted from pine and produced by DRT, registered under Reach regulation with CAS n°70750-57-l. The pine oil used is a product marketed under the trademark DERTOL® which is a terpenic alcohol extracted from pine as pine oil and produced by DRT, with terpenic alcohol content ranging from 88 to 93 wt. %, typically at 90 wt. %.

[0162] A composition of the invention as follows described is prepared according to the method of formulation.

[0163] Table 2

[0164] The composition described in table 2 is prepared as follows.

[0165] A thickener premix solution is prepared:

[0166] - lg of Benzothiazolinone into 974g of Water.

[0167] -Under agitation, 25g of Xanthan Gum is dispersed, andstirred until fully swollen and no lumps to form the thickener premix solution.

[0168] Pre-mixing before milling:

[0169] - The Anionic surfactant 1 is solubilized into Terpenic alcool;

[0170] - Then at room temperature, Water and the pH regulator are added and the mixture is stirred until a homogeneous emulsion is obtained.

[0171] - To the mixture is added glycerol, propylene glycol, Anionic surfactant 2, and then the mixture is stirred until a homogeneous mixture is obtained.

[0172] - Under agitation is then dispersed the sulfur, and the anti-foam agent is added.

[0173] - The mixture is stirred until the agglomerates disappear and then Milling with DYNO-MILL to the desired particle size;

[0174] Typically, the desired particle size is:

[0175] - Median diameter (pm) ranging from 0 to 3.2;

[0176] - Refusal passing 90% (pm) ranging from 0 to 8;

[0177] - Reject sieve 75 pm (%) ranging from 0 to 0.1; - Reject sieve 100 pm (%) ranging from 0 to 0.

[0178] - To the mixture obtained from the milling step above is added the terpenic oligomers, water and the thickener Premix solution previously prepared.

[0179] - The final mixture is stirred until complete dissolution.

[0180] - The final mixture has following physico-chemical characteristics:

[0181] - A pH at 20°C ranging from 7 to 9;

[0182] - A density at 20°C ranging from 1.41 to 1.43 g / ml;

[0183] - A Viscosity ford cup 4 at 20°C (s) ranging from 60 to 80;

[0184] - A Sulfur content (g / L) ranging from 690 to 790.

[0185] Example 1

[0186] Example 1 evaluates the impact of a co-formulation of the invention combining terpenic oligomer and terpenic alcohol when use during a fertilize treatment of wheat to reduce phytotoxicity due to nitrogen solution fertilizer.

[0187] Experimental conditions are:

[0188] Trial location: Poland

[0189] Crop: wheat

[0190] Experimental design by randomized complete block, with untreated included, 4 numbers of replications

[0191] Foliar application spray volume: 200L / ha

[0192] The applications of phytosanitary products follow the growth stages of the plant (BBCH).

[0193] 2 applications (Tl: BBCH 31 and T2: BBCH 39)

[0194] Table 3: (0 % - no phytotoxicity , 100 % - totally destroyed plant)

[0195] Results were calculated statistically according to ARM 10.0. The efficacy was calculated according to Abbott's formula). 11

[0196] The results in table 3 show that phytotoxicity symptoms occur with nitrogen treatment even at first application. Symptoms are higher with an overdose of 25% of nitrogen solution.

[0197] Table 3 demonstrates that in all cases, the addition of the composition comprising the coformulation composition of the invention with a terpenic oligomer and a terpenic alcohol reduce these symptoms. Furthermore, the phytotoxicity reduction seems linked to the dosage of co-formulation of the invention added.

[0198] More particularly, the phytotoxicity occurs after second application with standard dose. The addition of the composition comprising the co-formulation composition of the invention reduces significantly phytotoxicity severity and a dose effect is visible.

[0199] Example 2

[0200] Example 2 evaluates the impact of a composition comprising the co-formulation composition of the invention on apple tree to reduce phytotoxicity due solution fertilizer based on calcium chloride or calcium formate.

[0201] Experimental conditions are:

[0202] Trial location: Poland

[0203] Crop: Apple

[0204] Variety: Gala

[0205] Experimental design by randomized complete block, with 4 untreated plots included, 4 numbers of replications, plot size 18m2.

[0206] Foliar application spray with a boom P23, spray volume: 500L / ha

[0207] The applications of phytosanitary products follow the growth stages of the plant (BBCH).

[0208] There are 8 applications A: BBCH 67 / B: BBCH 69 / C: BBCH 71 / D: BBCH 71-72 / E: BBCH 72 / F: BBCH 73 / G: BBCH 74 / H: BBCH 75-76

[0209] The test's conditions are presented in table 4 below. Table 4

[0210] Table 5: (0 % : no phytotoxicity , 100 %: totally destroyed plant)

[0211] Results were calculated statistically according to ARM 10.0. The efficacy was calculated according to Abbott's formula).

[0212] The results of table 5 illustrate that a composition comprising a co-formulation of the invention allows in all cases the decrease of the phytotoxicity due solution fertilizer based on calcium chloride or calcium formate.

[0213] Example 3

[0214] Example 3 evaluates the phytotoxicity assessment of two sulfur based fungicide formulations (reference formulation with terpenic alcohols alone and tested formulation with terpenic alcohol and terpenic oligomers) on apple tree.

[0215] Experimental conditions are:

[0216] Trial location: South France

[0217] Crop: Apple

[0218] Variety: Golden

[0219] Trial was performed according to randomized complete block design, with 4 replicates. Plot size was 27.0 m2.

[0220] 9 applications were made every 7-10 days using a knapsack sprayer. Spray volume ranged from 400 to 500 L / ha. During bud to flowering stages, when the crop is the most susceptible with young leaves, 5 applications were performed. The other applications were made during fruit growing stage.

[0221] Phytotoxicity was assessed from 7 days after second application to harvest. Phytotoxicity symptoms were described and their intensity (%) was recorded. During bud to flowering stages, thermal amplitude ranged from 4.3 to 22.2°C. This amplitude exceeded 20°C in 7 days. Just after the third application when maximum phytotoxicity was recorded, thermal amplitude was 20.0-22.2°C during three consecutive days.

[0222] Under these weather conditions these susceptible crop stages, the reference formulation with terpenic alcohols alone caused high phytotoxicity, more than 10 % (see dotted line in Fig. 1).. Maximum phytotoxicity reached 14 %, after the third application when a high thermal amplitude was recorded. These observed phytotoxicity levels are not acceptable. Observed phytotoxicity consisted of necrosis on leaves. Later during fruit growing stage, phytotoxicity level was decreasing. This decrease was due to foliage development, older leaves less susceptible and early fall of affected leaves (see Figure 1).

[0223] The tested formulation with terpenic alcohols and terpenic oligomers, presented a lower phytotoxicity level remaining acceptable below 10 % during bud to flowering stage (see dashed line in Fig. 1). As reference formulation, the phytotoxicity was decreasing during fruit growing stage. Its phytotoxicity level was less than that of reference product until phytotoxicity level became very low (see Figure 1).

[0224] It is reasonable to conclude that the tested formulation (terpenic alcohols and terpenic oligomers) presents a better selectivity than the reference formulation (terpenic alcohols alone) on apple trees, especially under adverse conditions (susceptible cultivar, applications in early stages, high thermal amplitudes).

Claims

CLAIMS1. A co-formulation composition comprising a terpenic oligomer and a terpenic alcohol.

2. Co-formulation composition according to claim 1, wherein the weight ratio of terpenic alcohol to terpenic oligomer ranges from 0.5 to 8, preferably from 0.8 to 6, more preferably from 1 to 4.

3. Co-formulation composition according to any one of claim 1 or 2, wherein the terpenic oligomer is a molecule containing from 2 to 20 of terpenic structural units, wherein the terpenic structural units correspond to any terpene derived from hydrocarbon isoprene (CsHs)n with n a number ranging from 1 to 8.

4. Co-formulation composition according to any one of the preceding claims, wherein terpenic oligomer is obtained from a plant such as tree and typically from conifers, in particular from pine trees.

5. Co-formulation composition according to any one of the preceding claims, wherein the terpenic alcohol is a terpen having one or more primary, secondary or tertiary alcohol, preferably selected from the group consisting of 2,6-dimethyloct-7-en-2-ol, 4(8)-p-menthen- l-ol, cis-3,7-dimethyl-2,6-octadien-8-ol, trans-3,7-dimethyl-2,6-octadien-l-ol, 10- hydroxymethylene-2-pinene, 3,7-dimethyloct-6-en-l-ol and terpineol isomers such as alpha terpineol, beta terpineol, gamma terpineol, delt terpineol, terpinene-4-ol and a mixture thereof.

6. Co-formulation composition according to any one of the preceding claims, wherein the terpenic alcohol is obtained from plant such as a citrus oils or pine terpenes.

7. A phytosanitary and / or biostimulant composition comprising a co-formulation composition according to any one of claims 1 to 6 and one or more phytosanitary and / or biostimulant active substance(s).

8. Composition according to claim 7, the composition comprising from 1 to 10 wt. % of terpenic oligomer, preferably from 2 to 8 wt. % of terpenic oligomer and more preferably from 3 to 6 wt. % of terpenic oligomer, expressed by weight relative to the weight of the composition.

9. Composition according to any one of claim 7 or 8, the composition comprising from 10 to70 wt. % of active substance(s), preferably from 30 to 65 wt. % of active substance(s) and morepreferably from 50 to 60 wt. % of active substance(s) with respect to the total weight of composition.

10. Composition according to any one of claims 7 to 9, the composition comprising an active substance selected from the group consisting of insecticide, bactericide, fungicide, insect repellent or attractant and mixtures thereof.

11. Composition according to any one of claims 7 to 10, wherein the active substance is selected from the group consisting of sulfur, copper such as copper hydroxide, copper sulfate, copper oxychloride, pelargonic acid, orange essential oil and a mixture thereof.

12. Composition according to any one of claims 7 to 11, comprising one or more ingredients selected from the group consisting of a surfactant anionic or not, a polyol, glycerol, an antifoam agent, a pH regulator and a mixture thereof.

13. Composition according to any one of claims 7 to 12, wherein the composition comprises terpenic alcohol from 1 to 10 wt. %, preferably of 2,6-dimethyloct-7-en-2-ol; terpenic oligomer from 1 to 10 wt. %, preferably Derphalin®; active substance from 20 to 70 wt. %, preferably selected from the group consisting of sulfur, copper such as copper hydroxide, copper sulfate, copper oxychloride, pelargonic acid, orange essential oil and a mixture thereof; and eventually one or more of ingredients selected from the group consisting of: anionic surfactant from 1 to 2 wt. %, preferably tristyrylphenol anionic; and / or polyol from 1 to 5 wt. %, preferably propylene glycol; and / or non-ionic surfactants from 1 to 20 wt.%, and / or glycerol from 1 to 5 wt. %, preferably from 2 to 4 wt. % of propylene glycol and from 1 to 3 wt. % of glycerol; and / or anti-foam agent from 0.01 to 1 wt. %, a silicon emulsion; and / or pH regulator from 0.1 to 1 wt.%, preferably sodium hydroxide; and / or and a mixture thereof; water qsp 100 wt. %.

14. Composition according to any one of claims 7 to 13, wherein the composition is formulated in the form of a liquid, suspension, an emulsion, a concentrated emulsion, a dispersion, a suspoemulsion, an emulsifiable concentrate or slurry of particles in an aqueous medium.

15. Use of a co-formulation composition according to any one of claims 1 to 6 for preparing a phytosanitary and / or biostimulant composition according to any one of claims 7 to 14.

16. Use of a co-formulation composition according to any one of claims 1 to 6 for improving- spray retention explained by sticker effect; and / or- rainfastness; and / or- active substance penetration in plant; and / or - delay of droplet drying; and / or- preservation against UV photodegradation; and / or- drift reduction;- reducing the phytotoxicity; and / or- enhancing the selectivity of the one or more phytosanitary and / or biostimulant active principle(s).

17. A method of treating plant by application of a phytosanitary and / or biostimulant composition according to any one of claims 7 to 14.

18. A method of preparation of a phytosanitary and / or biostimulant composition according to any one of claims 7 to 14.

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